JP2710796B2 - Method for producing polyolefin resin composition - Google Patents

Description

The present invention relates to a polyolefin resin modified by reacting a copolymer of an alkenylsilane and an olefin with a compound containing a C 又 は C or C ＝ O double bond. It relates to a method for producing the composition.

[Prior Art] Olefin polymers are inexpensive and have a relatively good balance of physical properties, and are therefore used for various purposes. Various improvements have also been made on the random or block copolymerization of olefins for the purpose of improving the balance of physical properties.

[Problems to be solved by the invention]

However, olefin polymers are characterized by poor adhesion to polymers containing polar groups, metals, etc. due to their essence, and poor adhesion to paints, further expanding the applications of polyolefins. Therefore, attempts have been made to improve physical properties by introducing a polar group into polyolefin.

However, in ethylene, it is possible to copolymerize with a monomer containing a polar group by radical polymerization by high-pressure polymerization, but in other polyolefins, when a polar group-containing monomer is radically grafted to the polyolefin, Only the particular method that was said was successful.
The present inventors have previously attempted to modify a polyolefin by treating a copolymer of alkenylsilane and olefin with a compound that reacts with a Si—H bond (Japanese Patent Application No.
-26528), in this method, if an attempt is made to increase the amount of a compound that reacts with a Si-H bond,
When the obtained composition was used for molding, it was difficult to modify the polyolefin with good reproducibility, for example, it could not be molded due to poor flowability or could not be used by mixing with other olefins.

[Means for solving the problem]

The present inventors have diligently studied a method for producing a modified polyolefin resin composition by solving the above problems, and have reached the present invention.

That is, the present invention dissolves a copolymer obtained by copolymerizing an olefin and an alkenylsilane using a catalyst composed of a transition metal catalyst and an organometallic compound under heating in a solvent that dissolves the copolymer, At a temperature lower than the temperature at which the copolymer is dissolved, the copolymer is reacted with C in the presence of a hydrosilylation catalyst.
A method for producing a polyolefin resin composition, comprising subjecting a compound containing a C or C ＝ O double bond to a contact treatment.

In the production of the composition of the present invention, first, a copolymer of alkenylsilane and olefin is produced. The production of the copolymer can be achieved by polymerizing alkenyl silane and olefin in the presence of a known catalyst composed of a transition metal compound and an organometallic compound. The production of alkenylsilane and α-olefin copolymers by polymerization below is disclosed in US Pat. No. 3,223,686.

Here, the alkenyl silane may be vinyl silane, allyl silane, butenyl silane, pentenyl silane, a compound in which one or two Si-H bonds of these monomers are substituted with an alkyl group, or one to three Si-H bonds. And the like.

In the present invention, as the α-olefin, ethylene, propylene, butene-1, pentene-1, hexene-1,
Examples thereof include 2-methylpentene-1 or a mixture thereof, and a mixture thereof with a small amount of an olefin having a larger number of carbon atoms.

As the catalyst comprising a transition metal compound and an organometallic compound used for producing the copolymer according to the present invention, not only those described in the above-mentioned U.S. Patents, but also many α-olefins whose properties have been improved since then disclosed Can be used without any trouble.

The polymerization method is generally a solvent method using an inert solvent, but a bulk polymerization method and a gas phase polymerization method can also be employed. Here, as the catalyst comprising the transition metal compound and the organometallic compound, titanium halide or vanadium halide is preferably used as the transition metal compound, and an organoaluminum compound is preferably used as the organometallic compound.
For example, electron donation of titanium trichloride obtained by reducing titanium tetrachloride with metallic aluminum, hydrogen or organoaluminum, or those obtained by modifying them with an electron donating compound, an organoaluminum compound, and optionally an oxygen-containing organic compound. Catalyst system composed of a volatile compound, a vanadium halide, or a catalyst system composed of vanadium oxyhalide and organoaluminum, or a carrier such as a magnesium halide, or a titanium halide or a halogen treated with an electron-donating compound. A catalyst system composed of a transition metal compound catalyst obtained by carrying vanadium halide and vanadium oxyhalide and an electron donating compound such as an organic aluminum compound and, if necessary, an oxygen-containing organic compound, or a reaction product of magnesium chloride and an alcohol. In hydrogen solvent And then insoluble in a hydrocarbon solvent by treating with a precipitant such as titanium tetrachloride, treating with an electron-donating compound such as an ester or ether if necessary, and then treating with a titanium halide. Examples include a catalyst system comprising the obtained transition metal compound catalyst, an organic aluminum compound, and, if necessary, an electron donating compound such as an oxygen-containing organic compound (for example, various examples are described in the following literature. Ziegler −Natta Catal
sts and Polymerization by John Boor Jr (Academic P
ress), Journal of Macromorecular Sience Reviews i
n Macromolecular Chemistry and Physics, C24 (3) 35
5-385 (1984) and C25 (1) 578-597 (1985)).

Here, as the electron donating compound, oxygen-containing compounds such as ethers, esters, orthoesters, and alkoxysilicon compounds are usually preferred, and alcohols, aldehydes, and water can also be used.

Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide.Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Examples of the halide include chlorine, bromine and iodine.

Here, the polymerization ratio of the alkenyl silane and the α-olefin is not particularly limited, but is usually alkenyl silane.
It is preferably about 30 mol% to 0.01 mol% for the catalytic activity during polymerization, or for the reaction between the copolymer and the unsaturated compound and its utilization, particularly about 10 mol% to 0.05 mol%. Is preferred.

The molecular weight of the polymer is not particularly limited, but is extremely high molecular weight, for example, the intrinsic viscosity measured at 135 ° C. tetralin solution is preferably not more than 3,
More preferably, the intrinsic viscosity is about 0.1 to 2.

In the present invention, the copolymer obtained by the above reaction is
First, it is dissolved in a solvent. As the solvent used here,
Preferably, a hydrocarbon compound having 6 to 12 carbon atoms, or a halogenated hydrocarbon compound in which a part to all of the hydrogen atoms are substituted with a halogen atom is preferably used.
It is dissolved by heating to 200C to 200C.

The solution is cooled after or prior to the addition of a compound containing a C ＝ C or C ＝ O double bond described below. The temperature after cooling is usually preferably 50 ° C. or lower from the viewpoint of preventing the cross-linking reaction from proceeding by a side reaction. Then, after the addition of a compound containing a C 又 は C or C ＝ O double bond, a hydrosilylation catalyst is added in a cooled state to carry out the reaction. The reaction is carried out by keeping the temperature between 40C and 40C.
Here, the compound containing a C ＝ C or C ＝ O double bond is preferably a compound containing a C ＝ C double bond. The group bonded to C ＝ C or C ＝ O is not particularly limited. For example, various compounds known as vinyl compounds and vinylidene compounds, and various compounds known as aldehydes and ketones can be preferably exemplified. Examples of the vinyl compound and the vinylidene compound include those containing a polar group such as carboxylic acid, carboxylic acid ester, nitro, sulfonic acid, etc. directly on a double bond or with a — (CH ₂ ) _n — group interposed therebetween, or a phenyl group. In addition to a general polar group-containing vinyl compound in which various polar groups are bonded, polymethylene oxide, polyethylene oxide, polyalkylene oxides such as polypropylene oxide,
A so-called macromer in which a silicone having an —SiO— bond is directly or indirectly bonded to a vinyl group can also be used.

Examples of the C-O-containing compound include aldehydes and ketones. Specific examples include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, and benzaldehyde, acetone, methyl ethyl ketone, and methyl propyl. Ketone, diethyl ketone, 2-hexanone, 3-hexanone, cyclohexanone, biacetyl,
Examples include acetophenone, benzophenone, and the like, and those in which some of the hydrogens are substituted with the above polar groups.

In contacting with the above compound, a known hydrosilylation catalyst, for example, a metal catalyst of Group VIII of the periodic table such as a triphenylphosphine complex of rhodium, chloroplatinic acid or a salt thereof (organic silicon compound chemistry, Makoto Kumada et al. It is necessary to have a radical initiator such as an azo compound and an amine such as triethylamine. Since the hydrosilylation reaction is relatively fast, the reaction proceeds sufficiently at a temperature around room temperature, but the reaction rate or side reaction can be controlled by cooling or heating as necessary, for example, by avoiding a crosslinking reaction.

The unreacted compound containing a C ＝ C or C ＝ O double bond after the contact treatment is usually removed by filtration, evaporation removal, washing or the like, but depending on the use of the composition, the unreacted compound may be removed. It is not necessary to completely remove the compound, and in some cases, some unreacted compounds may be left as they are to form a composition.

〔Example〕

 Hereinafter, the present invention will be further described with reference to Examples.

Example 1 A vibration mill equipped with four crushing pots having an internal volume of 4 and containing 9 kg of steel balls having a diameter of 12 mm was prepared. Under a nitrogen atmosphere, 200 g of magnesium chloride, 75 ml of di-n-butyl phthalate, and 40 ml of titanium tetrachloride were added to each pot and pulverized for 40 hours. 100 g of the co-ground product thus obtained was placed in a flask of 5 and treated with toluene 2.0 at 115 ° C. for 2 hours. Then, toluene was extracted at 90 ° C. and washed once with 4 heptane seven times to obtain a titanium catalyst. Analysis showed that it contained 1.9 wt% titanium.

Toluene in an autoclave with an internal volume of 5 under a nitrogen atmosphere
40 ml, the transition metal catalyst 50 mg, methylcyclohexyldimethoxysilane 0.05 ml, triethylaluminum 0.50 ml
Was added, and then 1200 g of 30 g of vinylsilane and 4 N of hydrogen were charged, and polymerization was carried out at 70 ° C. for 4 hours. Next, unreacted propylene and vinylsilane were purged, the powder was taken out and dried, and then weighed and measured for physical properties.
The intrinsic viscosity (hereinafter abbreviated as η) of 0 g of the powder in a tetralin solution at 135 ° C. was 1.35, the vinylsilane content was 1.1 wt%, and strong absorption was observed at 2150 cm ⁻¹ in the infrared absorption spectrum. 10 g of this polymer was placed in a 200 ml flask, 100 ml of toluene was added, the mixture was dissolved by heating at 115 ° C. under a nitrogen atmosphere, and then cooled to 30 ° C., followed by polyethylene glycol monoallyl ether (Uniox PKA-5001 manufactured by NOF Corporation). After adding 50 ml and stirring, 0.05 g of a triphenylphosphine complex of rhodium chloride was added and 30
Stirred at C for 2 hours. After the reaction, the slurry was taken out and filtered, and the polymer was thoroughly washed with toluene. According to infrared absorption spectrum absorption of ethylene glycol was observed at 1100 cm ^-1, absorption of Si-H of 2150 cm ^-1 was reduced. The ratio of polypropylene and polyethylene glycol monoallyl ether calculated by elemental analysis was 1: 0.18. This polymer can be thermoformed by hot pressing at 230 ° C., and η obtained by polymerizing propylene with the above catalyst separately is 1.62, and the extraction residue obtained by extracting with boiling n-heptane for 6 hours with a Soxhlet extractor is used. Was mixed with polypropylene 100 having a ratio of 96.8% at a ratio of 10 and heated and molded. As a result, a uniform sheet was formed. This sheet did not show unevenness even when stretched at 150 ° C.

Comparative Example 1 Using the copolymer obtained in Example 1, 10 g of the polymer was added without dissolution, and 100 ml of toluene, 50 ml of polyethylene glycol monoallyl ether, and 0.05 g of a triphenylphosphine complex of rhodium chloride were added, followed by stirring at 80 ° C. for 2 hours. did. When analyzed in the same manner, the ratio of polypropylene to polyethylene glycol moallyl ether was 1: 0.08, but a uniform sheet was not obtained even when hot pressed at 230 ° C. When the sheet was stretched, the sheet was cut when stretched.

Example 2 A solution of chloroplatinic acid in tetrahydrofuran (0.05% as chloroplatinic acid) was obtained by using allylsilane instead of vinylsilane and using butyl acrylate (AB-6 manufactured by Toa Gosei Chemical Co., Ltd.) instead of polyethylene glycol monoallyl ether.
Except for using g), the same procedure as in Example 1 was carried out, and the ratio of butyl acrylate was 0.17. The obtained composition was moldable as in Example 1.

Example 3 A reaction was performed in the same manner as in Example 1 except that acetophenone was used instead of polyethylene glycol monoallyl ether, and the reaction was performed at 10 ° C. for 10 hours. The addition amount of acetophenone was 0.07. Molding was possible.

〔The invention's effect〕

By carrying out the method of the present invention, a composition containing a polar group is easily obtained and is extremely valuable industrially.

Claims (1)

(57) [Claims] 1. A copolymer obtained by copolymerizing an olefin and an alkenylsilane using a catalyst comprising a transition metal catalyst and an organometallic compound is dissolved in a solvent for dissolving the copolymer under heating, and then dissolved. At a temperature lower than the temperature at which the copolymer is dissolved and in the presence of a hydrosilylation catalyst,
Alternatively, a method for producing a polyolefin resin composition, comprising subjecting a compound containing a CＣO double bond to a contact treatment.